A typical effect of plasticization of glassy polymers in gas permeation is a minimum in the relationship between the permeability and the feed pressure. The pressure corresponding to the minimum is called the plasticization pressure. Plasticization phenomena significantly effect the membrane performance in, for example, CO2/CH4 separation processes. The polymer swells upon sorption of CO2 accelerating the permeation of CH4. As a consequence, the polymer membrane loses its selectivity. Fundamental understanding of the phenomenon is necessary to develop new concepts to prevent it.

In this paper, CO2-induced plasticization phenomena in 11 different glassy polymers are investigated by single gas permeation and sorption experiments. The main objective was to search for relationships between the plasticization pressure and the chemical structure or the physical properties of the polymer. No relationships were found with respect to the glass-transition temperature or fractional free volume. Furthermore, it was thought that polar groups of the polymer increase the tendency of a polymer to be plasticized because they may have dipolar interactions with the polarizable carbon dioxide molecules. But, no dependence of the plasticization pressure on the carbonyl or sulfone density of the polymers considered was observed. Instead, it was found that the polymers studied plasticized at the same critical CO2 concentration of 36±7 cm3 (STP)/cm3 polymer. Depending on the polymer, different pressures (the plasticization pressures) are required to reach the critical concentration.